Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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An Explanation of the Contrasting Reactivities of meso- and d,l-$D_3$-Trishomocubylidene-$D_3$-trishomocubane towards Electrophiles

  • Lee, Oh-Seuk (Department of Chemistry, Andong National University) ;
  • Osawa, Eiji (Department of Knowledge-Based Information Engineering, Toyohashi University of Technology)
  • Published : 1992.02.20
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Abstract

The contrasting behaviour of meso-and d,l-$D_3$-trishomocubylidene-$D_3$-trishomocubane (1 and 2) in the electrophilic addition reaction, the former giving rearranged spiro compound (1a and 1b) and the latter giving 1,2-adduct (2a and 2b), has been explained as arising from the secondary steric effects based on computational evidence. As the degree of out-of-plane deformation of the olefinic carbon atoms increases with reaction progress, the resulting internal congestion in the region behind the double bond becomes unbearably large in meso-1. The absence of symmetry plane across the double bond of d,l-2 helps for the closing fragments to adjust themselves.

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References

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